History of Semiconductors - National Institute of Telecommunications

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Invited paper
History of Semiconductors
Lidia Łukasiak and Andrzej Jakubowski
Abstract—The history of semiconductors is presented beginning with the first documented observation of a semiconductor
effect (Faraday), through the development of the first devices
(point-contact rectifiers and transistors, early field-effect transistors) and the theory of semiconductors up to the contemporary devices (SOI and multigate devices).
Keywords—band theory, laser, Moore’s law, semiconductor,
transistor.
1. Introduction
There is no doubt that semiconductors changed the world
beyond anything that could have been imagined before
them. Although people have probably always needed to
communicate and process data, it is thanks to the semiconductors that these two important tasks have become easy
and take up infinitely less time than, e.g., at the time of
vacuum tubes.
The history of semiconductors is long and complicated.
Obviously, one cannot expect it to fit one short paper.
Given this limitation the authors concentrated on the facts
they considered the most important and this choice is never
fully impartial. Therefore, we apologize in advance to all
those Readers who will find that some vital moments of
the semiconductor history are missing in this paper.
The rest of this paper is organized in four sections devoted
to early history of semiconductors, theory of their operation, the actual devices and a short summary.
2. Early History of Semiconductors
According to G. Busch [1] the term “semiconducting” was
used for the first time by Alessandro Volta in 1782. The
first documented observation of a semiconductor effect is
that of Michael Faraday (1833), who noticed that the resistance of silver sulfide decreased with temperature, which
was different than the dependence observed in metals [2].
An extensive quantitative analysis of the temperature dependence of the electrical conductivity of Ag2 S and Cu2 S
was published in 1851 by Johann Hittorf [1].
For some years to come the history of semiconductors focused around two important properties, i.e., rectification of
metal-semiconductor junction and sensitivity of semiconductors to light and is briefly described in Subsections 2.1
and 2.2.
2.1. Rectification
In 1874 Karl Ferdinand Braun observed conduction and
rectification in metal sulfides probed with a metal point
(whisker) [3]. Although Braun’s discovery was not immediately appreciated, later it played a significant role in the
development of the radio and detection of microwave radiation in WWII radar systems [4] (in 1909 Braun shared
a Nobel Prize in physics with Marconi). In 1874 rectification was observed by Arthur Schuster in a circuit made of
copper wires bound by screws [4]. Schuster noticed that
the effect appeared only after the circuit was not used for
some time. As soon as he cleaned the ends of the wires
(that is removed copper oxide), the rectification was gone.
In this way he discovered copper oxide as a new semiconductor [5]. In 1929 Walter Schottky experimentally confirmed the presence of a barrier in a metal-semiconductor
junction [5].
2.2. Photoconductivity and Photovoltaics
In 1839 Alexander Edmund Becquerel (the father of a great
scientist Henri Becquerel) discovered the photovoltaic effect at a junction between a semiconductor and an electrolyte [6]. The photoconductivity in solids was discovered
by Willoughby Smith in 1873 during his work on submarine cable testing that required reliable resistors with high
resistance [7]. Smith experimented with selenium resistors
and observed that light caused a dramatic decrease of their
resistance. Adams and Day were the first to discover the
photovoltaic effect in a solid material (1876). They noticed
that the presence of light could change the direction of the
current flowing through the selenium connected to a battery [8]. The first working solar cell was constructed by
Charles Fritts in 1883. It consisted of a metal plate and
a thin layer of selenium covered with a very thin layer of
gold [8]. The efficiency of this cell was below 1% [9].
3. Theory
In 1878 Edwin Herbert Hall discovered that charge carriers in solids are deflected in magnetic field (Hall effect).
This phenomenon was later used to study the properties
of semiconductors [10]. Shortly after the discovery of the
electron by J. J. Thomson several scientists proposed theories of electron-based conduction in metals. The theory of
Eduard Riecke (1899) is particularly interesting, because he
assumed the presence of both negative and positive charge
carriers with different concentrations and mobilities [1].
Around 1908 Karl Baedeker observed the dependence of
the conductivity of copper iodide on the stoichiometry (iodine content). He also measured the Hall effect in this material, which indicated carriers with positive charge [1]. In
1914 Johan Koenigsberger divided solid-state materials into
three groups with respected to their conductivity: metals,
3
Lidia Łukasiak and Andrzej Jakubowski
insulators and “variable conductors” [1]. In 1928 Ferdinand
Bloch developed the theory of electrons in lattices [10]. In
1930 Bernhard Gudden reported that the observed properties of semiconductors were due exclusively to the presence
of impurities and that chemically pure semiconductor did
not exist [1].
were caused by bad quality of the semiconductor. Therefore he melted the silicon in quartz tubes and then let it
cool down. The obtained material was still polycrystalline
but the electrical tests demonstrated that the properties were
much more uniform. Ohl identified the impurities that created the p-n junction that he accidentally obtained during
his technological experiments. He held four patents on silicon detectors and p-n junction [13].
4.3. Bipolar Transistor
Fig. 1. Alan Wilson’s theory of bands in solids.
In 1930 Rudolf Peierls presented the concept of forbidden gaps that was applied to realistic solids by Brillouin
the same year. Also in 1930 Kronig and Penney developed
a simple, analytical model of periodic potential. In 1931
Alan Wilson developed the band theory of solids based
on the idea of empty and filled energy bands (Fig. 1).
Wilson also confirmed that the conductivity of semiconductors was due to impurities [10]. In the same year Heisenberg developed the concept of hole (which was implicit in
the works of Rudolf Peierls [10]). In 1938 Walter Schottky and Neville F. Mott (Nobel Prize in 1977) independently developed models of the potential barrier and current flow through a metal-semiconductor junction. A year
later Schottky improved his model including the presence
of space charge. In 1938 Boris Davydov presented a theory of a copper-oxide rectifier including the presence of
a p-n junction in the oxide, excess carriers and recombination. He also understood the importance of surface
states [11]. In 1942 Hans Bethe developed the theory of
thermionic emission (Nobel Prize in 1967).
4. Devices
4.1. Point-Contact Rectifiers
In 1904 J. C. Bose obtained a patent for PbS point-contact
rectifiers [12]. G. Pickard was the first to show that silicon point-contact rectifiers were useful in detection of radio waves (patent in 1906) [10]. The selenium and copper
oxide rectifiers were developed, respectively, in 1925 by
E. Presser and 1926 by L. O. Grondahl [10]. The selenium rectifiers were heavily used in the WWII in military
communications and radar equipment [10].
4.2. The p-n Junction
During his work on the detection of radio waves Russel
Ohl realized that the problems with cat’s whisker detectors
4
In 1945 William Shockley put forward a concept of a semiconductor amplifier operating by means of the field-effect
principle. The idea was that the application of a transverse
electric field would change the conductance of a semiconductor layer. Unfortunately this effect was not observed experimentally. John Bardeen thought that this was
due to surface states screening the bulk of the material
from the field (Fig. 2). His surface-theory was published
in 1947 [14].
Fig. 2. The idea of surface states.
While working on the field-effect devices, in December
1947 John Bardeen and Walter Brattain built a germanium
point-contact transistor (Fig. 3) and demonstrated that this
device exhibited a power gain. There was, however, an
uncertainty concerning the mechanism responsible for the
transistor action [13]. Bardeen and Brattain were convinced
that surface-related phenomena had the dominant role in the
operation of the new device while Shockley favoured bulk
conduction of minority carriers. About one month later he
developed a theory of a p-n junction and a junction transistor [15]. Shockley, Bardeen and Brattain received the
Nobel Prize in physics in 1956 (John Bardeen received another one in 1972 for his theory of superconductivity). In
February 1948 John Shive demonstrated a correctly operating point-contact transistor with the emitter and collector
placed on the opposite sides of a very thin slice of germanium (0.01 cm). This configuration indicated that the
conduction was indeed taking place in the bulk, not along
the surface (the distance between the emitter and collector along the surface would be much longer) [15]. It was
only then that Shockley presented his theory of transistor
operation to the coworkers [15], [16].
It is worth remembering that the crucial properties of
semiconductors at the time were “structure sensitive”
History of Semiconductors
(as Bardeen put it in [14]), that is they were strongly dependent on the purity of the sample. The semiconductor material with which Bardeen and Brattain worked was
prepared using a technique developed by Gordon K. Teal
and John B. Little based on the Czochralski method. The
crystal was then purified using the zone refining method
proposed by William G. Pfann [11].
in 1960. In the same year Jean Hoerni proposed the planar transistor (both base and emitter regions diffused). The
oxide that served as a mask was not removed and acted as
a passivating layer [15].
Further improvement of speed was proposed by Herbert
Kroemer. A built-in electric field could be introduced into
the base by means of graded doping. Another way of introducing the electric field in the base he thought of was
grading the composition of the semiconductor material itself, which resulted in graded band gap. This heterostructure concept could not be put to practice easily because of
fabrication problems [17].
4.4. Integrated Circuit
Fig. 3. The first point-contact transistor [16].
Point-contact transistors were the first to be produced, but
they were extremely unstable and the electrical characteristics were hard to control. The first grown junction
transistors were manufactured in 1952. They were much
better when compared to their point-contact predecessor,
but the production was much more difficult. As a result
of a complicated doping procedure the grown crystal consisted of three regions forming an n-p-n structure. It had
to be cut into individual devices and contacts had to be
made. The process was difficult and could not be automated easily. Moreover, a lot of semiconductor material
was wasted. In 1952 alloyed junction transistor was reported (two pellets of indium were alloyed on the opposite
sides of a slice of silicon). Its production was simpler and
less material-consuming and could be automated at least
partially. The obtained base width was around 10 µ m,
which let the device operate up to a few MHz only. The
first diffused Ge transistor (diffusion was used to form the
base region, while the emitter was alloyed) with a characteristic “mesa” shape was reported in 1954. The base width
was 1 µ m and the cut-off frequency 500 MHz. It was generally understood that for most applications silicon transistors
would be better than germanium ones due to lower reverse
currents. The first commercially available silicon devices
(grown junction) were manufactured in 1954 by Gordon
Teal. The first diffused Si transistor appeared in 1955. To
reduce the resistivity of the collector that limited the operation speed without lowering the breakdown voltage too
much John Early thought of a collector consisting of two
layers, i.e., high-resistivity one on top of a highly doped
one. A transistor with epitaxial layer added was reported
The transistor was much more reliable, worked faster
and generated less heat when compared to the vacuum
tubes [18]. Thus it was anticipated that large systems could
be built using these devices. The distance between them
had, however, to be as short as possible to minimize delays
caused by interconnects. In 1958 Jack Kilby demonstrated
the first integrated circuit where several devices were fabricated in one silicon substrate and connected by means
of wire bonding. Kilby realized that this would be a disadvantage therefore in his patent he proposed formation
of interconnects by means of deposition of aluminum on
a layer of SiO2 covering the semiconductor material [15].
This has been achieved independently by Robert Noyce in
1959. In 2000 Jack Kilby received a Noble Prize in physics
for his achievements.
4.5. Tunnel Diode
Leo Esaki studied heavily doped junctions to find out how
high the base of a bipolar transistor could be doped before
the injection at the emitter junction became inadequate. He
was aware that in very narrow junctions tunneling could
take place. He obtained the first Ge tunneling diode in
1957 and a silicon one in 1958. Esaki’s presentation at the
International Conference of Solid State Physics in Electrons
and Telecommunications in 1958 was highly appreciated by
Shockley [19]. Unfortunately, Shockley exhibited a complete lack of interest when Robert Noyce came to him to
present his idea of a tunnel diode two years earlier. As a result Noyce moved to other projects [20]. The tunnel diode
was extremely resistant to the environmental conditions due
to the fact that conduction was not based on minority carriers or thermal effects. Moreover, its switching times were
much shorter than those of the transistor. Leo Esaki received a Nobel Prize in physics in 1973 for his work on
tunneling and superlattices [21], [22].
4.6. Metal-Oxide-Semiconductor Field-Effect Transistor
(MOSFET)
In 1930 and 1933 Julius Lilienfeld obtained patents for devices resembling today’s MESFET and MOSFET, respec5
Lidia Łukasiak and Andrzej Jakubowski
tively. In 1934 Oskar Heil applied for a patent for his
theoretical work on capacitive control in field-effect transistors [3].
The first bipolar transistors were quite unreliable because semiconductor surface was not properly passivated.
A group directed by M. M. Atalla worked on this problem
and found out that a layer of silicon dioxide could be the
answer [23]. During the course of this work a new concept of a field-effect transistor was developed and the actual
device manufactured [24]. Unfortunately, the device could
not match the performance of bipolar transistors at the time
and was largely forgotten [15]. Several years before Bell
Laboratories demonstrated an MOS transistor Paul Weimer
and Torkel Wallmark of RCA did work on such devices.
Weimer made transistors of cadmium sulfide and cadmium
selenide [11]. In 1963 Steven Hofstein and Fredric Heiman
published a paper on a silicon MOSFET [25] (Fig. 4). In
the same year the first CMOS circuit was proposed by Frank
Wanlass [26]. In 1970 Willard Boyle and George Smith
presented the concept of charge-coupled devices (CCD) –
a semiconductor equivalent of magnetic bubbles [27]. Both
scientists received a Nobel Prize in physics in 2009 for
their work on CCD.
It is estimated that gate leakage current increases approximately 30 times every technology generation, as opposed to
3–5 times increase of channel leakage current [36]. Apart
from leakage current, the reduction of gate-oxide thickness
increases the susceptibility of the device to boron penetration from the poly-Si gate into the channel. A number of
different high-k materials are extensively investigated.
Fig. 5. A cross section of a SOI MOSFET.
Fig. 4. A cross section of a metal-oxide-semiconductor transistor.
Early MOSFETs had aluminum gate. Development of
a poly-Si gate [28] led to a self-aligned device, where the
gate itself constitutes the mask for source and drain diffusion. In this way parasitic gate-to-source and gate-to-drain
capacitances associated with gate overlap could be controlled. Since polysilicon had relatively high resistance,
gates made of silicides of refractory metals were proposed
(e.g., [29], [30]).
Reduction of the size of the device led to the so-called
short-channel effects (SCE) including threshold voltage
roll-off and drain-induced barrier lowering. The ways to
cope with this problem include a reduction of the depth
of source and drain [31] combined with efforts to avoid
increased resistance (e.g., lightly doped drain [32], elevated source/drain (S/D) [33] or possibly Schottky barrier S/D [34]). Threshold voltage and punchthrough are
controlled by means of the appropriate doping profile of the
channel that makes it possible to maintain relatively good
surface mobility (e.g., [35]). Short-channel effects are considerably reduced when gate oxide is thin. As a result of
decreased thickness, gate leakage current obviously grows,
increasing power consumption of the entire chip, which is
an undesirable effect for battery-powered mobile systems.
6
Fig. 6. Mutigate transistors: (a) double gate; (b) FinFET; (c) surrounding gate.
History of Semiconductors
An interesting extension of the classical bulk MOSFET is
silicon-on-insulator (SOI) – see Fig. 5 [37]. The advantage
of SOI is the ease of electrical isolation of a device from
the rest of the integrated circuit, which increases packing
density. Moreover, the area of source and drain junctions
is significantly reduced, thus decreasing parasitic capacitances. Finally, the depletion width is limited by the Si
body thickness, therefore it is widely believed that SOI
helps reduce short channel effects unless source-to-drain
coupling through channel and BOX cannot be neglected.
The properties of SOI devices are improved with the reduction of body thickness. It is believed that fully depleted
ultra-thin-body SOI (FD UTB SOI) is one of the best scaling solutions. Due to excellent gate control of the channel
these devices may be undoped or very lightly doped. In
this way mobility is not degraded and threshold voltage
is less dependent on the fluctuations of doping concentration [38]. Another advantage of SOI is that it facilitates
development of new device concepts [39] (Fig. 6), but this
is another story.
4.7. Semiconductor Lasers
Semiconductors are widely used for emission and detection
of radiation. The first report on light emitted by a semiconductor appeared in 1907 in a note by H. J. Round. Fundamental work in this area was conducted, among other, by
Losev. A very interesting description of the development
of light-emitting diodes may be found in [40] while the
history of photovoltaics is discussed in [8]. In this section
only semiconductor lasers are mentioned briefly.
The first semiconductor lasers were developed around 1962
by four American research teams [41]. Further research in
this area went in two directions, i.e., wider spectrum of
materials to obtain wider wavelength range and concepts
of new device structures. Herbert Kroemer and Zhores
Alferov have independently come up with the idea that
semiconductor lasers should be built on heterostructures.
Zhores Alferov was a member of the team that created
the first Soviet p-n junction transistor in 1953. He was
directly involved in research aimed at development of specialized semiconductor devices for Russian nuclear submarines. The matter was of such importance for the Soviet
authorities that he used to receive phone calls from very
high government officials who wanted the work done faster.
To fulfill those requests Alferov had to move to the lab
and literally live there [42]. Later he worked on power
devices and became familiar with p-i-n and p-n-n structures. When the first report on semiconductor lasers appeared, he realized that double heterostructures of the
p-i-n type should be used in these devices [41]. He obtained the first practical heterostructure devices and the
first heterostructure laser [42]. In 2000 Alferov and Kroemer (mentioned in Subsection 4.4) received a Nobel Prize
in physics for their achievements in the area of semiconductor heterostructures used in high-speed- and optoelectronics.
Significant progress in semiconductor lasers is associated,
among other, with the use of quantum wells and new materials, especially gallium nitride.
5. Summary
Silicon may be considered as the information carrier of
our times. In the history of information there were two
revolutions (approximately 500 years apart). The first was
that of Johan Gutenberg who made information available to
many, the other is the invention of the transistor. Currently
the global amount of information doubles every year. Many
things we are taking for granted (such as, e.g., computers,
Internet and mobile phones) would not be possible without
silicon microelectronics. Electronic circuits are also present
in cars, home appliances, machinery, etc. Optoelectronic
devices are equally important in everyday life, e.g., fiberoptic communications for data transfer, data storage (CD
and DVD recorders), digital cameras, etc.
Since the beginning of semiconductor electronics the number of transistors in an integrated circuit has been increasing
exponentially with time. This trend had been first noticed
by Gordon Moore [43] and is called Moore’s law. This law
is illustrated in Fig. 7, where the number of transistors in
successive Intel processors is plotted as a function of time
(data after [44]).
Fig. 7. Number of transistors in successive Intel processors as
a function of time (data after [44]).
Even though the bipolar technology was largely replaced
by CMOS (more than 90 percent of integrated circuits are
manufactured in CMOS technology), Moore’s law is still
true in many aspects of the development trends of silicon
microelectronics (obviously, with the appropriate time constant). The MOS transistor has been improved countless
times but above everything else it has been miniaturized
7
Lidia Łukasiak and Andrzej Jakubowski
Fig. 8. Feature size as a function of time (data after [45]).
beyond imagination. The reduction of the feature size, presented in Fig. 8, is more or less exponential. The number
of transistors produced per year and the average price are
shown as a function of time in Fig. 9 (again the change is
exponential). It is being anticipated that in 2010 approximately one billion transistors will be produced for every
person living on the Earth.
Fig. 9. Number of transistors produced per year and transistor
price as a function of time (data after [46]).
We are pretty sure the future still holds a few surprises.
Extensive research is being carried out on graphene, organic
electronics, quantum devices, microsystems, integration of
silicon with other materials and many other issues, but that
is another story. . .
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Lidia Łukasiak graduated from
the Faculty of Electronics, Warsaw University of Technology,
Poland, in 1988 and joined
the Institute of Microelectronics
and Optoelectronics the same
year. She received the Ph.D. and
D.Sc. degrees from the same
university in 1994 and 2002,
respectively. Since 2004 she
has been the Vice-Director for
Teaching of the Institute of Microelectronics and Optoelectronics. Her research interests include modeling and characterization of semiconductor devices and microprocessor
systems.
e-mail: lukasiak@imio.pw.edu.pl
Institute of Microelectronics and Optoelectronics
Warsaw University of Technology
Koszykowa st 75
00-662 Warsaw, Poland
Andrzej Jakubowski received
the M.Sc., Ph.D. and D.Sc. degrees in electrical engineering
from the Warsaw University of
Technology (WUT), Poland. In
the years 1984–1990 and 1993–
2001 the Head of the Division
of Microelectronics of the Institute of Microelectronics and
Optoelectronics (IMiO) and in
the years 2001–2004 the Head
of the Division of Microelectronics and Nanoelectronics
Devices of IMiO. He was the Director of the Institute of
Electron Technology (ITE) in the years 1989–1992 and
Director of IMiO from 2004 till 2008. Between 1990 and
1991 he was the Chairman of the Committee of Applied
Research and a member of the Prime Minister’s Committee of Science and Technical Progress. He was the Vicechairman of the Committee of Electronics and Telecommunications of Polish Academy of Sciences between 1989
and 2007. He was also the Chairman of the Microelectronics Section of this Committee from 1988 till 2003.
He was the editor-in-chief of “Electron Technology” between 1990 and 1994. He is the author or co-author of
more than 600 publications (journal and conference papers, monographs) and several textbooks for students, as
well as popular-science papers. He delivered many invited
lectures at foreign universities and international conferences in Europe, United States and Asia. He supervised
23 Ph.D. theses and more than 150 B.Sc., and M.Sc. theses. He received 5 Awards of the Minister of National
Education. The main areas of his research are modeling,
characterization and fabrication of semiconductor structures
(e.g., MOS, SOI MOS, HBT, SiGe MOS).
e-mail: jakubowski@imio.pw.edu.pl
Institute of Microelectronics and Optoelectronics
Warsaw University of Technology
Koszykowa st 75
00-662 Warsaw, Poland
9
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